Hydrocarbon isomerization catalyst and process

ABSTRACT

A hydrocarbon isomerization catalyst composition, comprising a combination of catalytically effective amounts of a platinum or palladium component, an iridium component, a germanium component, a halogen component and a Friedel-Crafts metal halide component combined with a refractory inorganic oxide is disclosed. A specific example of the disclosed catalytic composition is a combination of catalytically effective amounts of a platinum component, an iridium component, a germanium component, a chloride component and an aluminum chloride component with an alumina carrier material, effective in isomerizing a pentane-hexane hydrocarbon fraction or in isomerizing non-equilibrium mixtures of alkylaromatic hydrocarbons such as xylenes.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation-in-part of my copending applicationSer. No. 365,782 filed May 31, 1973, now U.S. Pat. No. 3,839,193, Oct.1, 1974 which copending application is a continuation-in-part of mycopending application Ser. No. 27,457, filed Apr. 10, 1970, nowabandoned the teachings of both of which copending applications arespecifically incorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to a catalyst for isomerizing isomerizablehydrocarbons including isomerizable parraffins, cycloparafins, olefinsand alkylaromatics. This invention further relates to a process forisomerizing isomerizable hydrocarbons with a catalytic compositecomprising a combination of platinum or palladium component, an iridiumcomponent, a germanium component, a halogen component and aFridel-Crafts metal halide with a refractory inorganic oxide. Thepresent invention utilizes a dual-function catalytic composite havingboth a hydrogenation-dehydrogenation function and a cracking functionwhich affords substantial improvements in hydrocarbon isomerizationprocesses that have traditionally used dual-function catalysts.

Processes for the isomerization of hydrocarbons have acquiredsignificant importance within the petrochemical and petroleum refiningindustry. The demand for para-xylene has created a demand for processesto isomerize other xylene isomers and ethylbenzene to producepara-xylene. The demand for certain branched chain paraffins, such asisobutane or isopentane, as intermediates in producing high octane motorfuel alkylate, can be met by isomerizing the corresponding normalparaffins. It is desired that the alkylate be highly branched to providea high octane rating. This can be accomplished by alkylating anisoparaffin with C₄ -C₇ internal olefins which, in turn, can be producedby isomerization of corresponding linear alpha-olefins.

Catalytic composites exhibiting a dual hydrogenation-dehydrogenation andcracking function are widely used in the petroleum and petrochemicalindustry to isomerize hydrocarbons. Such catalysts generally have aheavy metal component, e.g., metals or metallic compounds of Group Vthrough VIII of the Periodic Table, to inpart ahydrogenation-dehydrogenation function, with an acid-acting inorganicoxide to import a cracking function. In catalysis of isomerizationreactions, it is important that the catalytic composite not onlycatalyze the specific desired isomerization reaction by having its dualhyrogenation-dehydrogenation function correctly balanced against itscracking function, but also that the catalyst perform its desiredfunctions well over prolonged periods of time.

The performance of a given catalyst in a hydrocarbon isomerizationprocess is typically measured by the activity, selectivity, andstability of the catalyst. Activity refers to the ability of a catalystto isomerize the hydrocarbon reactants into the corresponding isomers ata specified set of reaction conditions; selectivity refers to thepercent of reactants isomerized to form the desired isomerized productand/or products; stability refers to the rate of change of theselectivity and activity of the catalyst.

The principal cause is instability (i.e., loss of selectivity andactivity in an originally selective, active catalyst) is the formationof coke on the catalytic surface of the catalyst during the reaction.This coke is characterizable as a high molecular weight,hydrogen-deficient, carbonaceous material, typically having an atomiccarbon to hydrogen ratio of about 1 or more. Thus, a problem in thehydrocarbon isomerization art is the development of more active andselective composites not sensitive to the carbonaceous materials and/orhaving the ability to suppress the rate of the formation of thesecarbonaceous materials on the catalyst. A primary aim of the art is todevelop a hydrocarbon isomerization process utilizing a dual-functioncatalyst having superior activity, selectivity and stability. Inparticular, it is desired to provide a process wherein hyrocarbons areisomerized without excessive cracking or other decomposition reactionswhich lower the overall yield of the process and make it more difficultto operate.

SUMMARY OF THE INVENTION

It is an object of this invention to provide a catalyst compositionsuitable for use in a process for isomerizing isomerizable hydrocarbons.It is another object of this invention to provide an isomerizationprocess using a particular isomerization catalyst effective inisomerizing isomerizable hydrocarbons without introducing undesireddecomposition and/or cracking reactions. It is a further object of thisinvention to provide a process for isomerizing isomerizable hydrocarbonsutilizing a dual-function catalyst having superior activity, selectivityand stability.

An isomerization process has now been developed utilizing adual-function catalyst which possesses improved activity, selectivityand stability. Moreover, in the particular case of a C₈ alkylaromaticisomerization process, the present catalyst allows essentiallyequilibrium conversions of the C₈ alkylaromatics with essentiallystoichiometric selectivity without evidencing excessive production ofhydrogenated or cracked products. Further, this activity and selectivityis readily maintainable at its originally high levels, evidencing a verystable catalytic alkylaromatic isomerization process.

In a broad embodiment, this invention relates to a catalytic compositecomprising a refractory inorganic oxide having combined therewith, on aFriedel-Crafts metal halide-free basis, about 0.01 to about 2 weightpercent platinum or palladium, about 0.01 to about 2 weight percentiridium, about 0.01 to about 5 weight percent germanium, and about 0.1to about 3.5 weight percent halogen, calculated on an elemental basis,and about 1.0 to about 100 weight percent Friedel-Crafts metal halide,wherein the platinum or palladium, iridium and germanium are uniformlydispersed throughout the refractory inorganic oxide, whereinsubstantially all of the platinum or palladium and iridium are presentin the corresponding metallic states and wherein substantially all ofthe germanium is present in an oxidation state above that of theelemental metal.

In another broad embodiment, this invention relates to a process forisomerizing an isomerizable hydrocarbon which comprises contacting saidhydrocarbon at isomerization conditions with a catalytic compositecomprising a combination of a platinum or palladium component, asiridium component, a germanium component, a halogen component and aFriedel-Crafts metal halide component with a refractory inorganic oxidecarrier material.

In a more limited embodiment, this invention relates to a catalystcomposition which comprises a combination of a platinum component, aniridium component, a germanium component, a chlorine component and analuminum chloride component with an alumina carrier material.

In another more limited embodiment, this invention relates to anisomerization process utilizing a catalytic composite comprising acombination of a platinum or palladium component, an iridium component,a germanium component, a chlorine component and an aluminum chloridecomponent with an alumina carrier material, the components preferablybeing present in the composite in amounts sufficient to result in thefinal composite containing, on an elemental, Friedel-Crafts metalhalide-free basis, about 0.01 to about 2.0 weight percent platinum orpalladium metal, and about 0.01 to about 2 weight percent iridium metal,and about 0.01 to about 5 weight percent germanium and about 3.5 weightpercent chlorine, wherein the platinum or palladium, germanium andiridium are uniformly dispersed throughout the porous carrier material,wherein substantially all of the platinum or palladium and iridium arepresent in the corresponding elemental metallic state, whereinsubstantially all of the germanium is present in an oxidation stateabove that of the elemental metal.

In a more specific embodiment, this invention relates to theisomerization of either a saturated or olefinic isomerizable hydrocarbonby contacting the hydrocarbon with the catalytic composite of thepresent invention at isomerization conditions which include atemperature of about 0° to about 425°C., a pressure of about atmosphericto about 100 atmospheres and a liquid hourly space velocity of about 0.1to about 10. In another limited embodiment this process related to theisomerization of an isomerizable alkylaromatic hydrocarbon by contactingthe alkylaromatic with the catalytic composite of the present inventionat isomerization conditions which include a temperature of about 0° toabout 600°C., a pressure of about atmospheric to about 100 atmospheres,a liquid hourly space velocity of about 0.1 to about 20.0 hr.⁻ ¹ and ahydrogen to hydrocarbon mole ratio of about 1:1 to about 20:1.

Other objects and embodiments referring to alternative isomerizablehydrocarbons and to alternative catalytic compositions will be found inthe following further detailed description of this invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

The catalyst of this invention is useful in the isomerization ofisomerizable saturated hydrocarbons including acyclic paraffins andcyclic naphthenes and is particularly suitable for the isomerization ofstraight chain or mildly branched chain paraffins containing 4 or morecarbon atoms per molecule such as normal butane, normal pentane, normalhexane, normal heptane, normal octane, etc., and mixtures thereof.Cycloparaffins applicable are those containing at least 5 carbon atomsin the ring such as alkylcyclopentanes and cyclohexanes, includingmethylcyclopentane, dimethylcyclopentane, cyclohexane,methylcyclohexane, dimethylcyclohexane, etc. The catalyst of thisinvention is also useful for conversion of mixtures of paraffins and/ornaphthenes such as those derived by selective fractionation anddistillation of straight-run natural gasolines and naphthas. Suchmixtures of paraffins and/or naphthenes include the so-called pentanefractions, hexane fractions, and mixtures thereof. It is not intended,however, to limit this invention to these enumerated saturatedhydrocarbons and it is contemplated that straight or branched chainsaturated hydrocarbons containing up to about 20 carbon atoms permolecule may be isomerized using the catalyst of the present inventionwith C₄ -C₉ hydrocarbons being particularly preferred.

The olefins which may be isomerized using the present catalyst aregenerally mixtures of olefinic hydrocarbons of approximately the samemolecular weight, including the 1-isomer, 2-isomer and other positionisomers, capable of undergoing isomerization to olefins in which thedouble bond occupies a different position in the hydrocarbon chain. Thecatalyst of this invention can be used to provide an olefinic feedstockfor motor fuel alkylation purposes containing an optimum amount of themore centrally located double bond isomers, by converting the 1-isomer,or other near-terminal-position isomer into olefins wherein the doublebond is made centrally located in the carbon atoms chain. The catalystof this invention is useful for isomerizing such isomerizable olefinichydrocarbons as 1-butene or 3-methyl-1-butene, which are converted into2-butene and 2-methyl-2-butene, respectively. This invention can beutilized to shift the double bond of an olefinic hydrocarbon such as1-pentene, 1-hexene, 2-hexene or 4-methyl-1-pentene to a more centrallylocated position so that 2-pentene, 2-hexene, 3-hexene or4-methyl-2pentene, respectively, can be obtained. It is not intended tolimit this invention to the enumerated olefinic hydrocarbons. It iscontemplated that shifting the double bond to a different position maybe effective in straight or branched chain olefinic hydrocarbonscontaining up to about 20 carbon atoms per molecule. This invention alsoapplies to the hydroisomerization of olefins wherein olefins areconverted to branched-chain paraffins and/or branched olefins.

The catalyst of this invention is also useful for the isomerization ofisomerizable alkylaromatic hydrocarbons, e.g., ortho-xylene,meta-xylene, para-xylene, ethylbenzene, the ethyltoluenes, thetrimethylbenzenes, the diethylbenzenes, the triethylbenzenes, normalpropylbenzene, isopropylbenzene, etc., and mixtures thereof. Preferredisomerizable alkylaromatic hydrocarbons are the alkylbenzenehydrocarbons, particularly the C₈ alkylbenzenes, and non-equilibriummixtures of various C₈ aromatic isomers. Higher molecular weightalkylaromatic hydrocarbons such as the alkylnaphthalenes, thealkylanthracenes, the alkylphenanthrenes, etc., are also suitable.

The isomerizable hydrocarbons may be utilized as found in selectivefractions from various naturally-occurring petroleum streams, e.g., asindividual components or as certain boiling range fractions obtained bythe selective fractionation and distillation of catalytically crackedgas oil. This invention may be utilized for complete conversion ofisomerizable hydrocarbons when they are present in minor quantities invarious fluid or gaseous streams. The isomerizable hydrocarbons to beconverted using the catalyst of this invention need not be concentrated.For example, isomerizable hydrocarbons appear in minor quantities invarious refinery offstreams, usually diluted with gases such ashydrogen, nitrogen, methane, ethane, propane, etc. These offstreams,containing minor quantities of isomerizable hydrocarbons, are obtainedfrom various refinery installations including thermal cracking units,catalytic cracking units, thermal reforming units, coking units,polymerization units, dehydrogenation units, etc., and have in the pastbeen burned as fuel, since an economical process for the utilization ofthe hydrocarbon content has not been available. This is particularlytrue of refinery fluid streams which contain minor quantities ofisomerizable hydrocarbons. This invention allows the isomerization ofaromatic streams such as reformate to produce xylenes, particularlyparaxylene, thus upgrading the reformate from its gasoline value to ahigh petrochemical value.

As hereinbefore indicated, the catalyst of the present inventioncomprises a refractory inorganic oxide carrier material or supporthaving combined therewith catalytically effective amounts of a platinumor palladium component, an iridium component, a germanium component, anda Friedel-Crafts metal halide component and a halogen component.

Considering first the porous carrier material utilized in the presentinvention, it is preferred that the material be a porous, adsorptive,high-surface area support having a surface area of about 25 to about 500m² /g. The porous carrier material should be relatively refractory tothe conditions utilized in the present process, and it is intended toinclude within the scope of useable supports materials which havetraditionally been utilized in dual-function hydrocarbon conversioncatalysts such as: silica or silica gel, silicon carbide, clays, andsilicates including those synthetically prepared andnaturally-occurring, which may or may not be acid treated, for example,attapulgus clay, china clay, diatomaceous earth, fuller's earth,kaoline, kieselguhr, etc.; ceramics, porcelain, crushed firebrick,bauxite; refractory inorganic oxides such as alumina, titanium dioxide,zirconium dioxide, chromium oxide, zinc oxide, magnesia, thoria, boria,silica-alumina, silica-magnesia, chromia-alumina. alumina-boria,silica-zirconia, etc.; crystalline zeolitic aluminosilicates such asnaturally-occurring or synthetically-prepared mordentie and/orfaujasite, either in the hydrogen form or in a form which has beentreated with mulit-valent cations; spinels such as Mg Al₂ 0₄, Fe Al₂ 0₄,RnAl₂ 0₄, MnAl₂ 0₄ , CaAl₂ 0₄ and other like compounds having theformula MoAl₂ 0₃ wherein M is a metal having a valence of 2; and,combinations of elements from one or more of these groups. The preferredporous carrier materials for use in the catalyst employed in the presentprocess are refractory inorganic oxides containing chemically combinedhydroxyl groups such as those contained in silica and any of the otheraforementioned refractory inorganic oxides including the variouscrystalline aluminosilicates and clays, with best results obtained withan alumina carrier material. Suitable alumina materials are thecrystalline aluminas known as the gamma-, eta-, and theta-alumina, withgamma- or eta-alumina giving best results. In addition, in someembodiments the alumina carrier material may contain minor proportionsof other well known refractory inorganic oxides such as silica,zirconia, magnesia, etc.; however, the preferred support issubstantially pure gamma-, or eta-alumina. Preferred carrier materialshave an apparent bulk density of about 0.3 to about 0.7 g/cc. andsurface area characteristics such that the average pore diameter isabout 20 to 300 Angstroms, the pore volume is about 0.1 to about 1 cc/g.and the surface area is about 100 to about 500 m² /g. In general, bestresults are typically obtained with a gamma-alumina carrier materialwhich is used in the form of spherical particles having: a relativelysmall diameter (i.e., typically about 1/16 inch), an apprent bulkdensity of about 0.5 to about 0.6 g/cc., a pore volume of about 0.4ml/g., and a surface area of about 175 m² /g.

The preferred alumina carrier material may be prepared in any suitablemanner and may be synthetically prepared or natural occurring. Whatevertype of alumina is employed it may be activated prior to use by one ormore treatments including drying, calcination, steaming, etc., and itmay be in a form known as activated alumina, activated alumina ofcommerce, porous alumina, alumina gel, etc. For example, the aluminacarrier may be prepared by adding a suitable alkaline reagent, such asammonium hydroxide to a salt of aluminum such as aluminum chloride,aluminum nitrate, etc., in an amount to form an aluminum hydroxide gelwhich upon drying and calcining is converted to alumina. The aluminacarrier may be formed in any desired shape such as sheres, pills, cakes,extrudates, powders, granules, tablets, etc., and utilized in anydesired size. For the purpose of the present invention a particularlypreferred form of alumina is the sphere; and alumina spheres may becontinuously manufactured by the well known oil drop method whichcomprises: forming an alumina hydrosol by any of the techniques taughtin the art and preferably by reacting aluminum metal with hydrochloricacid, combining the resulting hydrosol with a suitable gelling agent anddropping the resultant mixture into an oil bath maintained at elevatedtemperatures. The droplets of the mixture remain in the oil bath untilthey set and form hydrogel spheres. The spheres are then continuouslywithdrawn from the oil bath and typically subjected to specific agingtreatments in oil and an ammoniacal solution to further improve theirphysical characteristics. The resulting aged and gelled particles arethen washed and dried at a relatively low temperature of about 150° toabout 205°C. and subjected to a calcination procedure at a temperatureof about 455°to about 750°C. for a period of about 1 to about 20 hours.This treatment effects conversion of the alumina hydrogel to thecorresponding crystalline gamma-alumina. See the teachings of U.S. Pat.No. 2,620,314 for additional details.

One essential constituent of the catalyst of the present invention is agermanium component. It is an essential feature of the catalyst thatsubstantially all of the germanium component is present in the catalystin an oxidation state above that of the elemental metal. This componentmay exist within the composite as a compound such as the oxide, sulfide,halide, oxychloride, aluminate, etc., or in combination with the carriermaterial or other ingredients of the composite. Although it is notintended to restrict the composition of the catalyst by thisexplanation, it is believed that best results are obtained when thegermanium component is present in the composite in the +2 or +4oxidation state, with the +4 oxidation state being preferred.Preferably, the germanium component is used in an amount sufficient toresult in the final catalytic composite containing, on an elemental,Friedel-Crafts metal halide-free basis, about 0.01 to about 5 weightpercent germanium with best results typically obtained with about 0.05to about 2 weight percent germanium.

This germanium component may be incorporated in the catalyst compositein any suitable manner known to the art to result in a uniformdispersion of the metal moiety throughout the carrier material, e.g., bycoprecipitation or cogellation with the porous carrier material,ion-exchange with the gelled carrier material, or impregnation of thecarrier material either after or before it is dried and calcined. Anyconventional method for uniformly distributing a metallic component in acatalytic composite may be employed. The particular method ofincorporation used is not deemed to be an essential feature of thepreparation of the composite. One method of incorporating the germaniumcomponent into the catalytic composite involves coprecipitating thegermanium component during the preparation of the preferred carriermaterial, alumina. This method typically involves the addition of asuitable germanium compound such as germanium tetrachloride or finelydivided germanium oxide to the alumina hydrosol and then combining thehydrosol with a suitable gelling agent and dropping the resultingmixture into an oil bath, etc., as explained in detail hereinbefore.After drying and calcining the resulting gelled carrier material thereis obtained an intimate combination of alumina and germanium oxide. Apreferred method of incorporating the germanium component into thecatalytic composite involves utilization of a soluble, decomposablecompound of germanium to impregnate the porous carrier material. Ingeneral, the solvent used in this impregnation step is selected on thebasis of its capacity to dissolve the desired germanium compound and ispreferably an aqueous, acidic solution. The germanium component may beadded to the carrier material by commingling the latter with an aqueous,acidic solution of suitable germanium salt or suitable compound ofgermanium such as germanium oxide, germanium tetraethoxide, germaniumtetrapropoxide, germanium tetrachloride, germanium difluoride, germaniumtetrafluoride, germanium di-iodide, germanium monosulfide and the likecompounds. One particularly preferred impregnation solution comprisesnascent germanium metal dissolved in chlorine water to yield a germaniumoxychloride. A second preferred impregnation solution comprisesgermanium tetrachloride dissolved in an anhydrous alcohol such asethanol or propanol. In general, the germanium component can beimpregnated either before, at the same time, or after the other metalliccomponents are added to the carrier material; however, excellent resultsare obtained when the germanium component is impregnated simultaneouslywith the other metallic components. A preferred impregnation solutioncomprises chloroplatinic acid, hydrogen chloride, chloroiridic acid andgermanium tetrachloride dissolved in ethanol. Best results are believedto be obtained when this component exists in the composite as germaniumoxide.

Regardless of which germanium compound is used in the preferredimpregnation step, it is important that the germanium component beuniformly distributed throughout the carrier material. In order toachieve this objective it is necessary to maintain the pH of theimpregnation solution in a range of about 1 to about 7 and to dilute theimpregnation solution to a volume which approximates the volume of thecarrier material which is impregnated. It is preferred to use a volumeratio of impregnation solution to carrier material of at least 0.5:1 andpreferably about 1:1 to about 10:1 or more. Similarly, it is preferredto use a relatively long contact time during the impregnation stepranging from about one quarter hour up to about one half hour or morebefore drying to remove excess solvent in order to insure a highdispersion of the germanium component through the carrier material. Themixture of impregnation solution and carrier material is, likewise,preferably constantly agitated during this preferred impregnation step.

A second essential ingredient of the catalyst is the platinum orpalladium component. The use of platinum or palladium, or mixturesthereof, as a second component of the present composite are included. Itis an essential feature of the catalyst that substantially all of thisplatinum or palladium component exists within the final catalyticcomposite in the elemental metallic state. Generally, the amount of thiscomponent present in the final catalyst composite is small compared tothe quantities of the other components combined therewith. In fact, theplatinum or palladium component generally will comprise about 0.01 toabout 2 weight percent of the final catalytic composite, calculated onan elemental, Friedel-Crafts metal halide-free basis. Excellent resultsare obtained when the catalyst contains about 0.05 to about 1 weightpercent of platinum or palladium metal.

This platinum or palladium component may be incorporated in thecatalytic composite in any suitable manner known to result in arelatively uniform distribution of this component in the carriermaterial such as coprecipitation or cogellation, ion-exchange, orimpregnation. The preferred method involves the utilization of asoluble, decomposable compound of platinum or palladium to impregnatethe carrier material in a relatively uniform manner. For example, thiscomponent may be added to the support by commingling the latter with anaqueous solution of chloroplatinic or chloropalladic acid. Otherwater-soluble compounds of platinum or palladium may be employed inimpregnation solutions. These include ammonium chloroplatinate,bromoplatinic acid, platinum dichloride, platinum tetrachloride hydrate,platinum dichlorocarbonyl dichloride, dinitrodiaminoplatinum, palladiumchloride, palladium nitrate, palladium sulfate, etc. The utilization ofa platinum or palladium chloride compound, such as chloroplatinic orchloropalladic acid, is preferred since it facilitates the incorporationof both the platinum or palladium component and at least a minorquantity of the preferred halogen component in a single step. Hydrogenchloride or the like acid is also generally added to the impregnationsolution in order to further facilitate the incorporation of the halogencomponent and the uniform distribution of the metallic componentthroughout the carrier material. In addition, it is generally preferredto impregnate the carrier material after it has been calcined in orderto minimize the risk of washing away the valuable platinum or palladiumcompounds; however, in some cases it may be advantageous to impregnatethe carrier material when it is in a gelled state.

Another essential ingredient of the catalyst composite is an iridiumcomponent. It is of fundamental importance that substantially all of theiridium component exist within the catalytic composite of the presentinvention in the elemental state and the subsequently describedreduction procedure is designed to accomplish this objective. Theiridium component may be utilized in the composite in any amount whichis catalytically effective, with the preferred amount being about 0.01to about 2 weight percent thereof, calculated on an elemental iridiumbasis. Typically best results are obtained with about 0.05 to about 1weight percent iridium. It is additionally preferred to select thespecific amount of iridium from within this broad weight range as afunction of the amount of the platinum or palladium component, on anatomic basis, as explained hereinafter.

The iridium component may be incorporated into the catalytic compositein any conventional manner which results in a relatively uniformdispersion of iridium in the carrier material. It may be added at anystage of the preparation of the composite, either during preparation ofthe carrier material or thereafter. The precise method of incorporationused is not critical. Best results are thought to be obtained when theiridium component is relatively uniformly distributed throughout thecarrier material, and the preferred procedures are those known to resultin a composite having this relatively uniform distribution. Oneacceptable preocedure for incorporating this component into thecomposite involves cogelling or coprecipitating the iridium componentduring the preparation of the preferred carrier material, alumina. Thisprocedure usually comprehends the addition of a soluble, decomposablecompound of iridium such as iridium tetrachloride to the aluminahydrosol before it is gelled. The resulting mixture is then finished byconventional gelling, aging,, drying and calcination steps as explainedhereinbefore. A preferred way of incorporating this component is animpregnation step wherein the porous carrier material is impregnatedwith a suitable iridium-containing solution either before, at the sametime as, or after the carrier material is calcined. Preferredimpregnation solutions are aqueous solutions of water soluble,decomposable iridium compounds such as iridium tribromide, iridiumdichloride, iridium tetrachloride, iridium oxalic acid, iridium sulfate,potassium iridochloride, chloroiridic acid and the like compounds. Bestresults are ordinarily obtained when the impregnation solution is anaqueous solution of chloroiridic acid or sodium chloroiridate. Thiscomponent can be added to the carrier material, either before, at thesame time as, or after the other metallic components are combinedtherewith. Best results are usually achieved when this component isadded simultaneously with the other metallic components. Excellentresults are obtained with a one-step impregnation procedure using anaqueous solution comprising chloroplatinic or chloropalladic acid,chloroiridic acid, hydrochloric acid and germanium tetrachloridedissolved in anhydrous alcohol.

It is essential to incorporate a halogen component into the catalyticcomposite of the present invention. Although the precise form of thechemistry of the association of the halogen component with the carriermaterial is not entirely known, it is customary in the art to refer tothe halogen component as being combined with the carrier material orwith the other ingredients of the catalyst in the form of the halide(e.g., as the chloride). This combined halogen may be either fluorine,chlorine, iodine, bromine, or mixtures thereof. Of these, fluorine and,particularly, chlorine are preferred for the purposes of the presentinvention. The halogen may be added to the carrier material in anysuitable manner, either during preparation of the support or before orafter the addition of the other components. For example, the halogen maybe added to the carrier at any stage of the preparation of the carriermaterial or after calcination as an aqueous solution of a suitable,decomposable, halogen-containing compound such as hydrogen fluoride,hydrogen chloride, hydrogen bromide, ammonium chloride, etc. The halogencomponent or a portion thereof, may be combined with the carriermaterial during the impregnation of the latter with the platinum orpalladium or iridium components e.g., by use of a mixture ofchloroplatinic acid and hydrogen chloride. In another embodiment, thealumina hydrosol which is typically utilized to form the preferredalumina carrier material may contain halogen and thus contribute atleast a portion of the halogen component to the final composite. It isgenerally preferred to utilize amounts of halogen in the catalyst ofless than about 10 weight percent halogen calculated on an elementalbasis, and more preferably about 0.1 to about 3.5 weight percent.

Regarding the preferred amounts of the various metallic components ofthe catalyst, the amounts of the iridium component and the germaniumcomponent may be specified as a function of the amount of the platinumor palladium component. On this basis, the amount of the iridiumcomponent is ordinarily selected so that the atomic ratio of iridium toplatinum or palladium metal contained in the composite is about 0.1:1 toabout 2:1, with the preferred range being about 0.25:1 to about 1.5:1.Similarly, the amount of the germanium component is ordinarily selectedto produce a composite containing an atomic ratio of germanium toplatinum or palladium metal of about 0.3:1 to about 10:1, with thepreferred range being about 0.6:1 to about 6:1.

The "total metals content" is defined to be the sum of the platinum orpalladium component, the iridium component and the germanium component,calculated on a Friedel-Crafts metal halide-free, elemental metal basis.Good results are ordinarily obtained with the subject catalyst when thetotal metals content is fixed at a value of about 0.15 to about 3 weightpercent, with best results ordinarily achieved at a metals loading ofabout 0.3 to about 2 weight percent.

Regardless of the details of how the above-described metals componentsof the catalyst are combined with the porous carrier material, theresulting composite generally will be dried at a temperature of about95° to about 315°C. for a period of at least about 2 to about 24 hoursor more, and calcined or oxidized at a temperature of about 370° toabout 595°C. in an air atmosphere for a period of about 0.5 to about 10hours in order to convert substantially all of the metallic componentssubstantially to the oxide form. Because a halogen component is utilizedin the catalyst, best results are generally obtained when the halogencontent of the catalyst is adjusted during the calcination step byincluding a halogen or a halogen containing compound in the airatmosphere utilized. In particular, when the halogen component of thecatalyst is chlorine, it is preferred to use a mole ratio of H₂ 0 to HC₁of about 5:1 to about 100:1 during at least a portion of the calcinationstep in order to adjust the final chlorine content of the calcinedcomposite to a range of about 0.1 to about 3.5 weight percent.

The resulting calcined composite is then impregnated with anotheressential ingredient of the catalyst of the present invention, theFriedel-Crafts metal halide component. Aluminum chloride is particularlypreferred for use as the Friedel-Crafts metal halide component in thepresent catalyst. Other suitable metal halides include aluminum bromide,ferric chloride, ferric bromide, zinc chloride, beryllium chloride, etc.

The presence of chemically combined hydroxyl groups in the refractoryinorganic oxide allows a reaction to occur between the Friedel-Craftsmetal halide and the hydroxyl group of the carrier material. Forexample, aluminum chloride reacts with the hydroxyl groups of thepreferred alumina carrier material to yield Al--O--AlCl₂ active centerswhich enhance the catalytic behavior of the composite. It is desiredthat the combined halogen component be present in the calcined compositewithin the lower end of the 0.1 to 10 weight percent halogen range. Thisrange of combined halogen content substitutes to some degree for thehydroxyl groups which are necessary for reaction of the carrier materialwith the Friedel-Crafts metal halide component. This prevents to a smallextent, reaction between the Friedel-Crafts metal halide and the carriermaterial. Some halogen must be present, however, in order to insure thatthe germanium component remains in its dispersed oxidation state in thecatalyst.

The Friedel-Crafts metal halide may be impregnated onto the calcinedcomposite containing combined hydroxyl groups by the sublimation of theFriedel-Crafts metal halide onto the calcined composite under conditionssuch that the sublimed Friedel-Crafts metal halide is combined with thehydroxyl groups of the calcined composite. This reaction is typicallyaccompanied by the elimination of about 0.5 to about 2.0 moles ofhydrogen chloride per mole of Friedel-Crafts metal halide reacted withthe carrier material. For example, in the case of subliming aluminumchloride, which sublimes at about 184°C., suitable impregnationtemperatures range from about 190° to about 700°C., with a preferablerange being between about 200° and about 600°C. The sublimation can beconducted at atmospheric pressure or under increased pressure and in thepresence or absence of diluent gases such as hydrogen or lightparaffinic hydrocarbons or both. The impregnation of the Friedel-Craftsmetal halide may be conducted batch wise, but a preferred method forimpregnating the calcined composite is to pass sublimed AlCl₃ vapors, inadmixture with an inert gas such as hydrogen, through a calcinedcatalyst bed. This method both continuously deposits and reacts thealuminum chloride and also removes the evolved HCl.

The amount of Friedel-Crafts metal halide combined with the calcinedcomposite may range from about 1 weight percent up to about 100 weightpercent of the Friedel-Crafts metal halide-free, calcined composite. Thefinal composite containing the sublimed Friedel-Crafts metal halide istreated to remove the unreacted Friedel-Crafts metal halide bysubjecting the composite to a temperature above the sublimationtemperature of the Friedel-Crafts metal halide for a time sufficient toremove from the composite any unreacted Friedel-Crafts metal halide. Inthe case of AlCl₃, temperatures of about 400° to about 600°C., and timesof from about 1 to about 48 hours are sufficient.

It is an essential feature of the catalyst employed in the process ofthe present invention that the resultant catalytic composite issubjected to a substantially water-free reduction step prior to its usein the isomerization of hydrocarbons. This step is designed to reducethe platinum or palladium and iridium components to the correspondingmetals selectively and to insure a uniform and finely divided dispersionof these metallic components throughout the carrier material, whilemaintaining the germanium component in a positive oxidation state.Preferably, substantially pure and dry hydrogen (i.e., less than 20 vol.ppm. H₂ 0) is used as the reducing agent in this step. The reducingagent is contacted with the catalyst at conditions including atemperature of about 435° to about 650°C. and a period of time of about0.5 to 2 hours effective to reduce substantially all of the platinum orpalladium and iridium components to their elemental metallic state whilemaintaining the germanium component in an oxidation state above that ofthe elemental metal. This reduction treatment may be performed in situas part of a startup sequence if precautions are taken to predry theisomerization unit to a substantially water-free state and ifsubstantially water-free hydrogen is used.

The resulting reduced catalytic composite may, in some cases, bebeneficially subjected to a presulfiding operation designed toincorporate in the catalytic composite from about 0.05 to about 0.5weight percent sulfur, calculated on an elemental, Friedel-Crafts metalhalide-free basis. Preferably, this presulfiding treatment takes placein the presence of hydrogen and a suitable sulfur-containing compoundsuch as hydrogen sulfide, lower molecular weight mercaptans, organicsulfides, etc. Typically, this procedure comprises treating theselectively reduced catalyst with a sulfiding gas such as a mixture ofhydrogen and hydrogen sulfide having about 10 moles of hydrogen per moleof hydrogen sulfide at conditions sufficient to effect the desiredincorporation of sulfur, generally including a temperature ranging fromabout 10° up to about 595°C. or more. It is generally a good practice toperform this presulfiding step under substantially water-freeconditions.

According to the present invention, an isomerizable hydrocarbon chargestock, preferably in admixture with hydrogen, is contacted with acatalyst of the type hereinbefore described in a hydrocarbonisomerization zone. Contacting may be effected using the catalyst in afixed bed system, a moving bed system, a fluidized bed system, or in abatch type operation. In view of the danger of attrition loss of thevaluable catalyst and of operational advantages, it is preferred to usea fixed bed system. In this system, a hydrogen-rich gas and the chargestock are preheated by suitable heating means to the desired reactiontemperature and then passed into an isomerization zone containing afixed bed of the catalyst type previously characterized. The conversionzone may be one or more separate reactors with suitable meanstherebetween to insure that the desired isomerization temperature ismaintained at the entrance to each zone. It is to be noted that thereactants may be contacted with the catalyst bed in either upward,downward, or radial flow fashion, and that the reactants may be in theliquid phase, a mixed liquid-vapor phase, or vapor phase when contactedwith the catalyst, with best results obtained in a vapor phase.

Isomerization of isomerizable olefinic or saturated hydrocarbons ispreferably effected in a continuous downflow fixed bed system. Onepreferred method is to pass the hydrocarbons continuously, preferablycommingled with about 0.1 to about 10 moles or more of hydrogen per moleof hydrocarbon, to an isomerization reaction zone containing thecatalyst, and to maintain the zone at proper isomerization conditionssuch as a temperature in the range of about 0° to about 425°C. or moreand a pressure of about atmospheric to about 100 atmospheres or more.The hydrocarbon is passed over the catalyst at a liquid hourly spacevelocity (defined as volume of liquid hydrocarbon passed per hour pervolume of catalyst) of from about 0.1 to about 10 hr..sup.⁻¹ or more. Inaddition, diluents such as argon, nitrogen, etc., may be present. Theisomerized product is continuously withdrawn, separated from the reactoreffluent, and recovered by conventional means, preferably fractionaldistillation, while the unreacted starting material may be recycled toform a portion of the feed stock.

Isomerization of an isomerizable alkylaromatic hydrocarbon is preferablyeffected by contacting the alkylaromatic, in a reaction zone containingthe hereinbefore described catalyst as a fixed catalyst bed by passingthe hydrocarbon in a down-flow fashion through the bed, whilemaintaining the zone at proper alkylaromatic isomerization conditionssuch as a temperature in the range from about 0° to about 600°C. ormore, and a pressure of atmospheric to about 100 atmospheres or more.The hydrocarbon is employed, preferably in admixture with hydrogen at ahydrogen to hydrocarbon mole ratio of about 1:1 to about 25:1 or more,and at a liquid hourly hydrocarbon space velocity of about 0.1 to about20 hr..sup.⁻¹ or more. Inert diluents such as nitrogen, argon, etc., maybe present. The isomerized product is continuously withdrawn, separatedfrom the reactor effluent by conventional means including fractionaldistillation or crystallization, and recovered.

The following working examples are given to illustrate further thepreparation of the trimetallic catalytic composite utilized in theprocess of the present invention and the employment of the catalyst inisomerization of hydrocarbons. It is to be understood that the examplesare illustrative rather than restrictive.

EXAMPLE I

This example demonstrates a particularly good method of preparing thepreferred catalytic composite utilized in the process of the presentinvention.

An alumina carrier material comprising 1/16 inch spheres is prepared byforming an aluminum hydroxyl chloride sol by dissolving substantiallypure aluminum pellets in a hydrochloric acid solution, addinghexamethylenetetramine to the resulting sol, gelling the resultingsolution by dropping it into an oil bath to form spherical particles ofan aluminum hydrogel, aging and washing the resulting particles andfinally drying and calcining the aged and washed particles to formspherical particles of gamma-alumina containing about 0.3 weight percentcombined chloride. Additional details as to the method of preparing thepreferred carrier material are given in the teachings of U.S. Pat. No.2,620,314.

A measured amount of germanium tetrachloride is dissolved in anhydrousethanol. The resulting solution is then aged at room temperature untilan equilibrium condition is established therein. An aqueous solutioncontaining chloroplatinic acid, chloroiridic acid and hydrogen chlorideis then prepared. The two solutions are then intimately admixed and usedto impregnate the gamma-alumina particles in amounts, respectively,calculated to result in a final composite containing, on an elementalbasis, 0.375 weight percent platinum, 0.375 weight percent iridium and0.5 weight percent germanium. In order to insure uniform distribution ofthe metallic components throughout the carrier material, the amount ofhydrogen chloride corresponds to about 2 weight percent of the aluminaparticles. This impregnation step is performed by adding the carriermaterial particles to the impregnation mixture with constant agitation.In addition, the volume of the solution is approximately the same as thevolume of the carrier material particles. The impregnation mixture ismaintained in contact with the carrier material particles for a periodof about one-half hour at a temperature of about 21°C. Thereafter, thetemperature of the impregnation mixture is raised to about 108°C. andthe excess solution is evaporated during a period of about one hour. Theresulting dried particles are then subjected to a calcination treatmentin an air atmosphere at a temperature of about 496°C. for about 1 hour.The calcined spheres are then contacted with an air stream containing H₂0 and HC0 in a mole ratio of about 40:1 for about 4 hours at 524°C. inorder to adjust the halogen content of the catalyst particles to a valueof about 0.90. The resulting particles are analyzed and found tocontain, on an elemental basis, about 0.375 weight percent platinum,about 0.375 weight percent iridium, about 0.5 weight percent germaniumand about 0.85 weight percent chloride. The atomic ratio of germanium toplatinum is found to be 3.56:1, and the atomic ratio of iridium toplatinum is found to be 1.02:1. The calcined particles are placed in aglass lined rotating autoclave along with anhydrous aluminum chloridewhich is added to the autoclave in the amount of 3 parts, by weight, ofaluminum chloride for each 4 parts of the calcined catalyst particlesadded. The autoclave is sealed, pressured with 25 psig. of hydrogen, andheated and rotated for 2 hours at 300°C. The autoclave is then allowedto cool and is decompressed through a caustic scrubber, opened and thefinal composite removed therefrom. An analysis of the composite removedfrom the autoclave indicates about a 15 weight percent gain based on theoriginal calcined composite, indicating an amount of aluminum chloridesublimed onto the catalyst of an equivalent weight percent. The causticscrubber is found to have adsorbed hydrogen fluoride equivalent to about5.0 weight percent of the calcined composite, which corresponds to about0.8 moles of HCl evolved per mole of aluminum chloride reacted with thecalcined composite.

Thereafter, the resulting catalyst particles are subjected to a dryprereduction treatment designed to reduce the platinum and iridiumcomponents to the elemental state, while maintaining the germaniumcomponent in a positive oxidation state, by contacting the composite forone hour with a substantially pure hydrogen stream which contains lessthan 5 volume ppm. H₂ 0 at a temperature of about 565°C. and a pressureslightly above atmospheric. A flow rate of the hydrogen stream throughthe catalyst particles is used which corresponds to a gas hourly spacevelocity of about 720 hrs.⁻ ¹.

EXAMPLE II

A portion of the catalyst prepared in Example I is placed, as acatalytic composite, in a continuous flow, fixed bed isomerization plantof conventional design. The charge stock, containing on a weight percentbasis, 20.0 percent ethylbenzene, 10.0 percent para-xylene, 50.0 percentmeta-xylene, and 20.0 percent ortho-xylene is commingled with about 8moles of hydrogen per mole of hydrocarbon, heated to 400°C., andcontinuously charged at 4.0 hr..sup.⁻¹ liguid hourly space velocity(LHSV) to the reactor which is maintained at a pressure of about 400psig. and 400°C. The resulting product evidences essentially equilibriumconversion to para-xylene with only insignificant amounts of crackedproducts thus indicating an efficient alkylaromatic isomerizationcatalyst.

EXAMPLE III

A portion of the catalyst produced by the method of Example I is placedin a continuous flow, fixed bed isomerization plant of conventionaldesign as utilized in Example II. Substantially pure meta-xylene is usedas a charge stock. The charge stock is commingled with about 8 moles ofhydrogen per mole of hydrocarbon, heated to about 390°C., andcontinuously charged to the reactor which is maintained at a pressure ofabout 300 psig. Substantial conversion of meta-xylene to para-xylene isobtained . . . i.e., greater than 80 percent of equilibrium.

EXAMPLE IV

A catalyst identical to that produced in Example I but containing only0.40 weight percent combined chloride, on an elemental Friedel-Craftsmetal halide-free basis, is used to isomerize 1-butene in an appropriateisomerization reactor, at a reactor pressure of about 500 psig. and areactor temperature of about 140°C. Substantial conversion to 2-buteneis observed.

EXAMPLE V

The same catalyst as utilized in Example IV is charged to anappropriate, continuous isomerization reactor of conventional designmaintained at a reactor pressure of about 1000 psig. and a reactortemperature of about 180°C. 3-methyl-1-butene is continuously passed tothis reactor with substantial conversion to 2-methyl-2-butene beingobserved.

EXAMPLE VI

A catalyst, identical to that catalyst produced in Example I except thatthe gamma-alumina particles are contacted with hydrogen fluoride toprovide a 2.9 weight percent combined fluoride content in the catalyst,is placed in an appropriate continuous isomerization reactor ofconventional design maintained at a reactor pressure of about 300 psig.and a reactor temperature of about 200°C. Normal hexane is continuouslycharged to the reactor and an analysis of the product stream showssubstantial conversion to 2,2-dimethylbutane,2,3-dimethylbutane,2-methylpentane, and 3-methylpentane.

EXAMPLE VII

A portion of the catalyst prepared in Example I is placed in anappropriate continuous isomerization apparatus and used to isomerizenormal butane at a reactor pressure of 300 psig., a 0.5 hydrogen tohydrocarbon mole ratio, a 1.0 liquid hourly space velocity, and areactor temperature of 230°C. Substantial conversion of normal butane toisobutane is observed . . . i.e., approximately a conversion of normalbutane to isobutane of about 45 weight percent of the original butanecharged.

EXAMPLE VIII

A portion of the catalyst prepared in Example I is placed in anappropriate continuous isomerization reactor maintained at a reactortemperature of about 210°C. and a reactor pressure of about 250 psig.Methylcyclopentane is continuously passed to this reactor with asubstantial conversion to cyclohexane being observed.

I claim as my invention:
 1. A catalytic composite consisting essentiallyof a refractory inorganic oxide having combined therewith, on aFriedel-Crafts metal halide-free basis, about 0.01 to about 2 weightpercent platinum or palladium, about 0.01 to about 2 weight percentiridium, about 0.01 to about 5 weight percent germanium, and about 0.1to about 3.5 weight percent halogen in halide form, calculated on anelemental basis, and about 1.0 to about 100 weight percentFriedel-Crafts metal halide, wherein the platinum or palladium, iridiumand germanium are uniformly dispersed throughout the refractoryinorganic oxide, wherein substantially all of the platinum or palladiumand iridium are present in the corresponding metallic states and whereinsubstantially all of the germanium is present in the form of the oxide,sulfide, halide, oxychloride or aluminate.
 2. A composite as defined inclaim 1 wherein the Friedel-Crafts metal halide is anhydrous aluminumchloride.
 3. A composite as defined in claim 2 wherein the refractoryinorganic oxide is alumina.
 4. A composite as defined in claim 1 whereinthe halogen is in chloride form.
 5. A composite as defined in claim 1wherein the atomic ratio of germanium to platinum or palladium containedin the composite is about 0.3:1 to about 10:1.
 6. A composite as definedin claim 1 wherein the atomic ratio of iridium to platinum or palladiumcontained in the composite is about 0.1:1 to about 2:1.
 7. A compositeas defined in claim 1 wherein the catalytic composite is sulfided tocontain about 0.05 to about 0.5 weight percent sulfur, calculated on anelemental, Friedel-Crafts metal halide-free basis.
 8. A composite asdefined in claim 1 wherein substantially all of the germanium is presentin the catalytic composite as germanium oxide.
 9. A composite as definedin claim 1 wherein the composite contains, on a Friedel-Crafts metalhalide-free, elemental basis, about 0.05 to about 1 weight percentplatinum, about 0.05 to about 1 weight percent iridium, about 0.05 toabout 2 weight percent germanium and about 0.5 to about 1.5 weightpercent halogen.